Treating damaged living human hair with water soluble polymerizable vinyl monomers



United States Patent TREATING DAMAGED LIVING HUMAN HAIR WITH WATER SOLUBLE POLYMERIZABLE VINYL MONOMERS Robert A. Wall, Darien, and Percy Fainer, Ridgefield, Conn., assignors to Clairol Incorporated, New York, N.Y., a corporation of Delaware No Drawing. Filed Sept. 27, 1965, Ser. No. 490,690

Int. Cl. A61k 7/06 US. Cl. 132-7 9 Claims ABSTRACT OF THE DISCLOSURE A process for strengthening and conditioning overporous hair by polymerizing in said hair a water soluble polymerizable monomeric vinylic compound having acid groups and then bridging the polymer chains so formed with a bridging agent to reduce the water solubility of the polymer chains.

This invention relates to compositions of matter useful for strengthening and reconditioning overporous or otherwise damaged hair and to processes or procedures for employing such compositions. More particularly, it relates to compositions and processes or procedures of these types which are useful in treating living human hair on the head of a subject.

It is known that excessive treatment of hair with various oxidizing, reducing, or swelling agents, such as those which are employed in coloring or shaping hair, often leave the hair in a weakened, overporous state with a harsh texture to the hand. In addition, this overporous state with a harsh texture to the hand. In addition, this overprocessed hair is often fragile, rubbery and mushy when wet.

In an effort to restore the original strength, texture and body of the hair, it has been suggested to use preparations whose basic components are oils, fats, waxes or protein hydrolyzates. These materials are rubbed into the porous hair but are not further fixed as permanent reinforcing or otherwise strengthening agents in the hair fibers. Because of this looseness of incorporation in the hair, these agents are relatively easily washed from the hair with conventional shampoos.

It is an object of the present invention to provide compositions of matter designed to restore the original strength, texture and body to hair which is overporous or otherwise damaged.

It is also an object of the present invention to provide processes or procedures designed to restore the original strength, texture and body to hair which is overporous or otherwise damaged.

It is a further object of the present invention to provide compositions of matter and processes or procedures designed to recondition overporous or otherwise damaged living human hair which has been brought to this condition by excessive treatment with various oxidizing, reducing, swelling agents or the like.

It is still a further object of the present invention to provide compositions and processes or procedures set forth in the above objects in which the beneficial results obtained from these are relatively long lasting.

Other and more detailed objects of this invention will be apparent from the following description and claims.

It has now been found that overporous or otherwise damaged hair may be strengthened and reconditioned in a manner which renders these beneficial changes relatively permanent. These changes are brought about by treating hair with a polymerizable material of a character and under conditions which permanently incorporates solid insoluble polymeric reinforcing material in the hair that is not removed by shampooing. It is observed in the practice of this invention that overporous or otherwisedamaged hair, after treatment with the present compositions, is not only stronger, but also firmer and less rubbery when wet. Moreover, it has a smoother texture, higher luster, improved control properties and enhanced water set retention when dry.

In accordance with the present invention hair which is overporous or otherwise damaged is treated with a polymerizable vinylic monomer having an acid forming group. The vinylic monomer taken up by the hair is polymerized, and the polymer chain so formed is rendered less soluble by the action of a bridging agent capable of bridging polymer chains together.

Although applicants do not want to be bound by any theory, it is believed that the vinylic monomer because of the relatively small size of the molecule and the conditions of treatment penetrates into the interior of the hair structure. Inside the hair structure the vinylic monomer is polymerized to relatively long chain molecules which because of their size cannot readily leave the interior of the hair structure. Furthermore, the action of the polymer chain bridging agent further insolu-bilizes the polymer chains and locks them within the hair structure. This action serves to restore the overporous or otherwise damaged hair to a condition resembling the natural condition of the hair.

The processes of the present invention may be practiced by applying the polymerizable vinylic monomer and bridging agent either serially or simultaneously. In the serial procedure the polymerizable vinylic monomer is first applied and allowed to partially or totally polymerize. The bridging agent is then applied to complete the treatment and to lock the polymer inside the hair structure.

When the polymerizable vinylic monomer and bridging agent are used simultaneously, they are preferably simply dissolved in one solution and applied to the hair.

The polymerization of the vinylic monomer may be brought about by heat as, for example, by passing a hot comb through the hair saturated with vinylic monomer. In another procedure a polymerization catalyst system, e.g., redox catalyst, or other free radical forming system, may be used to initiate and accelerate the polymerization or make it capable of proceeding at lower temperatures that can be tolerated by the human subject.

It is also advantageous, in accordance with the present invention, to use in conjunction with the polymerizable vinylic compound and/ or bridging agent a material which will facilitate the entry of these materials into the hair. For this purpose it is useful to use alkaline solutions of the treating agents which promote the swelling of the hair, and the entry of the active ingredients.

As mentioned above, it is a feature of the present invention to utilize a polymerizable vinylic: monomer having acidforming groups. These acid forming groups are important for the purposes of the present invention in that they provide cities at which neighboring polymer chains may be bridged b means of bridging agents utilized in this invention to render the polymer less soluble. As used herein, the term acid forming groups is intended to encompass the acid groups per se, the salts of these acids, as well as groups which will be converted into acid groups or salts under the conditions of use of the present invention.

In general, however, the polymerizable vinylic compounds that may be used in accordance with the present invention to further insolubilize the polymerized vinylic formula:

Rz( 3=C-X wherein R R and R are selected from the group consisting of hydrogen, alkyl, aryl, halide and X is selected from the group consisting of acid groups and salts thereof (e.g., COOH, SO H). By way of illustration, the following polymerizable vinylic compounds may be mentioned: acrylic acids, sodium acrylate, monoethanolamine acrylate, potassium acrylate, calcium acrylate, methacrylic acids, sodium methacrylate, monoethanolamine methacrylate, potassium methacrylate, calcium methacrylate, itaconic acid, and salts of itaconic acids.

The bridging agents used in accordance with the present invention to further insolubilize the polymerized vinylic compounds formed can be of a variety of types. One of the preferred classes of bridging agent comprises watersoluble compounds (i.e., salts, hydroxides, oxides, etc.) of elements of Group II or III of the Periodic Table capable of yielding multivalent cations (divalent, trivalent, etc. cations). These are believed to function as bridging agents through the formation of a salt like structure involving the acid groups of neighboring polymeric chains and the cations of the bridging agents. These bridges can be visualized in the case wherein the polymerizable vinylic compounds is a carboxylic acid compound, and the bridging agent is a calcium salt or other calcium compound as follows:

wherein A is a polymeric chain. Although only one bridge is illustrated in the Formula 2 between the polymeric chains, is should be understood that there can be many such bridges. By way'of illustration the following compounds can serve as bridging agents which will supply the cationic type bridge: CaCl ZnCl BaCl Al (SO and difunctional quaternary ammonium compounds such as: N-Tallow, N,N-dimethyl-N'-N-N'-trimethyl 1,3-propylene diammonium chloride (Aliquat 726); N-Tallow-1,3- propylenediaminedioleate (Diam 26 Dioleate).

Another class of bridging agent that may be used in accordance with the present invention may be described as agents capable of providing long chain organic monovalent cation. The mechanism by which these long chain cations work to provide a bridge between neighboring polymer chains is not quite clear. However, it is believed that this probably involves chain entanglement. By way of illustration this class bridging agent may be exemplified by the mono functional alkyl quaternary ammonium compounds or alkyl primary amines, e.g. cetyl pyridinium chloride; cetyl trimethylammonium chloride; stearyl amide.

As mentioned above, in one form of the Present invention, a catalyst system is provided to facilitate the polymerization of vinylic monomer. This is particularly useful in those aspects of the present invention in which the polymerization is to be effected at relatively low temperatures. The catalysts employed are those which are capable of producing free radicals to initiate the polymerization.

A variety of catalyst systems are useful in this connection. These usually take the form of a redox system involving the combination of an oxidation agent and a reducing agent. By way of illustration the following redox catalyst systems useful for the present purposes may be mentioned: (NH )S O /NaHSO H O /Fe+ S O /RSH; Fe /H50 Ce+ /R-OH; KmmO /citric acid.

In accordance with the present invention, as mentioned above, to facilitate the penetration of the active materials into the hair, it is useful to incorporate a swelling agent in the treating compositions. These materials are generally basic in nature and give the treating solutions a relatively high pH. A pH between 8 and 9 or 10 is particularly suitable for this purpose. However, a pH of between 7 and 11 will also serve the present purposes.

Any of a number of bases both organic and inorganic may be used to obtain the suitable pH. By way of example the following may be mentioned: monoethanolamine, NaOH, KOH, NH Ca(OH) The concentration of vinylic monomer, bridging agent, catalyst or initiator system (when employed) and time of treatment that are utilized in accordance with the present invention are interrelated and may be varied considerably. Any combination of these parameters which result in the incorportion into the hair structure of a polymer of high enough molecular weight to reinforce the hair strength will serve the purposes of this invention. This will be made clearer by a discussion of the mechanism of the polymerization reaction believed to be operating in the present invention.

The rate of conversion of monomer to polymer is made up of three steps: initiation, propagation, and termination. The initiation step consists of forming monomer free radicals, either by direct activation, or by forming other free radicals which then add to monomer. The rate of formation of monomer radicals (initiation) will be proportional to the monomer concentration and also the concentration of initiating radicals (which will in turn be proportional to initiator concentrations).

The propagation step will be primarily dependent on monomer concentration. This is the step which, relative to the initiation and termination steps, determines the molecular weight of the polymer formed (i.e., if propagation is fast compared to the termination and initiation steps, the molecular weight of the polymer formed will be high).

The rate of the termination step is proportional to the total concentration of all radicals; initiator, monomer, and growing chain species. (See, for example, P. J. Flory, Principles of Polymer Chemistry, Cornell University Press, 1953, chapter 4.)

From the above considerations, it is seen that a high rate of conversion of monomer to polymer may be obtained with high monomer and initiator concentrations, but this must be balanced off against the lower molecular weight of polymer obtained at high rates of conversion (when the initiation and termination stops are fast compared to the propagation step). If much of the polymer is of low molecular weight, then the reinforcing action of the polymer will be reduced.

Moreover, for practical purposes, the time of treatment cannot be unduly long. This must be taken into consideration in determining the concentration of the components of the compositions utilized in this invention, since the time interval during which a proper degree of polymerization takes place in dependent on the concentration of the various components of the composition. The concentration of vinylic monomer and catalyst system is therefore selected so that a sufficient degree of polymerization will take place so as to reinforce the hair within a time period generally used in the beauty trade for treating hair on the human head.

In general, however, the concentration of vinylic monomer present in the solution used either serially with the bridging agent and/or simultaneously with the bridging agent will be in the range of .05 M to 2.5 M.

The bridging agent is generally used in the concentration range of .05 M to 2.5 M, the divalent bridging agent usually being employed in the range of .05 M to 1.25 M and the monovalent agent in the range of .1 M to 2.5 M.

As mentioned above, the concentration of the catalyst can also vary. In general, however, it will fall in the range of from .0005 M to .025 M.

In the case wherein the catalyst comprises a two component system, the relative amounts of each component may also vary. The pH of the composition will generally be the governing factor. Where, for example, the composition has a pH of from about 8 to 9, the molar ratio of oxidizing agent to reducing agent will ordinarily be greater than 1 and falling in the range of about 1:1 to 13:1 and preferably about 1:1 to 3:1. Where, however, the pH is or higher, the reducing agent may even be dispensed with.

The time during which the vinylic polymerization is allowed to proceed will also vary. In general, however, this will be between 5 to 60 minutes. In the case where a hot comb is used in the treatment, the polymerization is practically instantaneous.

When the bridging agent is used simultaneously with the vinylic monomer, it, obviously, will be allowed to act over the same period of time as the vinylic monomer. However, where the bridging agent is applied after the application of the vinylic monomer, it is permitted to remain in contact with the hair over a period of 1 to 10 minutes and ideally for 5 minutes.

In one typical process of practicing the present invention, the treating solution is prepared immediately before use. The hair on the subjects head is saturated with the single solution containing all of the ingredients mentioned above, and the excess solution is combed out of the hair. The hair may then be left uncovered while the treating solution is doing its work or it may be covered with a towel or plastic turban. To hasten the action of the treating solution, the subject may be placed under a dryer or other source of heat.

The time duration over which the treating solution is allowed to act on the hair will vary with the original condition of the hair, temperature, composition, effect desired, etc. In general, however, in this aspect of the invention, the treatment will last for 10 to 30 minutes. The hair is then lightly rinsed off with lukewarm water and is ready for further cosmetic procedures at the option of the user, e.g., setting with pins or rollers and drying.

In another typical process for practicing the present invention, the materials are applied to the head in two steps. In the first step the polymerizable vinylic polymer and catalyst system are applied to the hair, and the polymerization is allowed to proceed for a period of time. Following this the bridging agent is applied to complete the process.

When the procedure is to be carried out in two steps, a more active catalyst or initiator system can be used. This is possible because without the bridging agent a precipitate will not form before the solution is worked into the hair. This is due to the fact that, although some polymer is formed before application to the hair, this polymer remains soluble in the absence of the bridging agent. As in the one step process, the treating solution (which does not in this case contain bridging agent) is poured through the hair, and the excess is combed out. After the desired time interval, e.g., 10 to 30 minutes, the hair is lightly rinsed, and a solution of bridging agent is poured through the hair and allowed to remain for 2 to 10 minutes. The hair is rinsed again and is ready for further procedures (as setting, etc.)

In the general procedure for the hot comb technique, an uncatalyzed solution of monomer and bridging agent is applied to the hair after the hair has been shampooed, but before the hair is dried. After the solution has been on the head for at least 10 minutes, the hair is slightly rinsed with water and dried. At this point the hair is ready for straightening with a hot comb and curling with a hot curling iron. The polymerization takes place during the hot comb and iron procedures.

The active ingredients utilized in the present invention may be applied in any suitable form. Thus, they may be applied as solutions, gels, creams, foams, lotions, etc.

In addition to the principal active ingredients described above, the composition utilized in the present invention may also contain other ingredients and particularly those which facilitate the application of the active ingredients to the hair. Thus, for example, a surfactant may be included to enhance the wetting property of the formulas employed. Non-ionic surfactants are particularly suitable in compositions which are used in connection with the hot comb technique.

The following examples are further illustrative of the present invention. It is to be understood, however, that the invention is not limited thereto.

EXAMPLE 1 The following four aqueous solutions were mixed together immediately before use and applied to hair at room temperature by wetting and combing through:

Percent by wt.

1 molar monoethanolamine acrylate (brought to pH 9.0 with monoethanolamine) (5.0 ml.) 9.6 2 /2% (NH S O (0.2 ml.) .004 0.1% NaHSO (0.1 ml.) .0001 25% CaCl (1.0 ml.) 3.6

After the hair had been wet with the above composite aqueous solution for 20 minutes, it was rinsed lightly with lukewarm water. The wet tensile modulus of hair, which had been subjected to three 2-h0ur bleaches with a commercial hair lightener and with three Protinators, was increased by approximately 25% after the above treatment.

A comparison of the water set waving efficiencies (as measured by the method of D. H. Kirby, Proc. Scientific Section, T.G.A., p. 12, No. 26 [December 1956]), of samples of untreated and treated hair as described above and hair set with a commercial setting lotion (all previously bleached) measured as a function of time after placing in a 23 C., relative humidity environment shows the following results:

Waving Efficiencies, Percent Initial 5 Min. 10 Min. 20 Min.

Untreated (Control) 96 50 40 34 Commercial Setting Lotion 96 60 42 38 Treate (l) 96 70 58 50 Treated (5) 96 70 58 56 EXAMPLE 2 A treating solution was prepared by mixing the following aqueous solutions:

Percent by wt. I

1 molar monothanolamine methacrylate (brought to pH 9.0 with monoethanolamine) (5.0 ml.) 2 /2% (NH S O (1.0 ml.) .004 25% CaCl 1.0 ml.) 3.6 0.1% NaHSO (0.5 ml) .0001

This composite solution was applied to hair using the procedure described in Example 1.

EXAMPLE 3 The following mixture was placed on some hair which had been bleached for 6 hours with 20 vol. H 0

Percent by weight 5.0 g. Sodium Acrylate 20 0.1 g. NaHSO .4 0.5 g. (NH4)2S203 1.0

25 ml. Water.

After 15 minutes the hair was rinsed with water and wet with a solution of 1 gram of CaCl (anhydrous) in 20 ml. of water. After 2 to 3 minutes the hair was rinsed in water again and dried. The tensile modulus index for the untrelaged hair was 4.0 while the value for the treated hair was The above treatment took place in two steps. The first step involved polymerizing the monomer, and the second step, the crosslinking of the polymer with the divalent 101'1S.

EXAMPLE 4 Hot comb technique The following mixture has been tested by applying it to hair to be straightened by the hot comb technique. The tests are half-head trials carried out in the following manner: The entire head is shampooed and towel dried and then the side to be treated is saturated with a solution containing:

Percent by weight 9.0 g. Sodium Acrylate 8.5 6.5 g. CaCl 6.1 0.2 g. Pluronic F68* .2 90 ml. H O.

*Pluronic F68 (MW. 8000) is a condensate of ethylene oxide with a. hydrophobic base formed by condensing propylene oxide with propylene glycol. After 10 minutes the entire head is rinsed lightly and then placed under the hot air dryer. When the hair is dry, the hair is combed with a hot comb and curled with a hot curling iron. What has been observed is the following: On most of the heads, the treated side had the following qualities as compared to the nutreated side: more sheen, smoother, more bounce, better combability, and took a longer processing time to straighten when chemical relaxers were used later on (indicating that the treated hair was less porous).

What is claimed is:

1. A process for reconditioning damaged hair which comprises wetting said hair with an aqueous solution containing by weight, 9.6% monoethanolamine acrylate, .004% (NHQ S O .0001% NaHSO and 3.6% CaCl and allowing said solution to remain in contact with said hair for 10 to 30 minutes to cause said acrylate and CaCl to form a water insoluble bridged polymer, said solution having a pH of about 9.

2. A process for reconditioning damaged hair which comprises wetting said hair with an aqueous solution containing by weight about 10.5% monoethanolamine methacrylate, .004% (NH S O 3.6% CaCl and .000l% of NaHSO and allowing said solution to remain in contact with said hair for 10 to 30 minutes to cause said methacrylate and CaCl to form a water insoluble bridged polymer, said solution having a pH of about 9.

3. A process for reconditioning damaged hair which comprises wetting said hair with an aqueous solution containing by weight 20% sodium acrylate, .4% NaHSO and 1% (NH S O for sufiicient time to permit polymerization of said acrylate and then wetting said hair with a 5% by weight aqueous solution of CaCl for to 30 minutes to permit the bridging of said polymerized acrylate.

4. A process for reconditioning damaged hair which comprises wetting said hair for a period of about 10 to 30 minutes with an aqueous solution containing by weight about 20% sodium acrylate, .4% NaHSO and 1% (NH S O and then wetting said hair for a period of about 1 to 10 minutes with about a 5% by weight aqueous solution of CaCl 5. A process for reconditioning damaged hair which comprises wetting said hair with an aqueous solution containing by weight 8.5% sodium acrylate and 6.1% CaCl and subjecting the hair so treated to heat.

6. A process for reconditioning damaged hair which comprises wetting said hair with an aqueous solution containing by weight about 8.5% of sodium acrylate and 6.1% CaCl for a period of about 10 to 30 minutes and then subjecting the hair so treated to heat to polymerize and bridge said sodium acrylate.

7. A polymerizable composition of matter comprising an aqueous solution containing by weight about 9.6% monoethanolamine acrylate, .0004% (NH4)2S208, .0001% NaHSO and 3.6% C-aC1 8. A polymerizable composition of matter comprising an aqueous solution containing by weight 10.5 monoethanolamine methacrylate, .004% (NI-1.9 8 0 .0001% NaHSO and 3.6% CaCl 9. A process for strengthening and reconditioning overporous and damaged hair which comprises treating said hair for a period of from about 5 to 60 minutes with an aqueous composition containing:

(a) a water soluble polymerizable vinylic monomer selected from the group consisting of acrylic acid, sodium acrylate, monoethanolamine acrylate, potassium acrylate, calcium acrylate, methacrylic acid, sodium methacrylate, monoethanolamine methacrylate, potassium methacrylate, calcium methacrylate and itaconic acid in the concentration range of about 0.5 M to 2.5 M;

(b) a bridging agent selected from the class consisting of CaCI ZnCl BaCl Al (SO N-tallow, N,N-dimethyl-N,N',N'-trimethyl-1, 3-propylene diammonium chloride and N-tallow-l, 3-propylenediamine-dioleate in the concentration range of from about .05 M to 2.5 M and (c) a redox catalyst system selected from the group consisting of S20g/NaHSO3; H O /Fe+ S O /RSH; Fe /H80 Ce' /R-OH and KmnO citric acid in the concentration range of .0005 M to .025 M.

References Cited UNITED STATES PATENTS 2,335,454 11/1943 Schuster et al 167-87.1 X 2,667,473 1/1954 Morner et al. l67--87.1 X 2,818,362 12/1957 Drechsel 16787.1 X 2,890,094 6/1959 Tucker 167-88 X 2,961,431 11/1960 Kutner 16787.1 X

FOREIGN PATENTS 535,040 2/1955 Belgium. 1,151,940 7/1963 Germany. 1,160,983 1/1964 Germany. 1,162,509 2/ 1964 Germany. 36/23,650 12/1961 Japan.

224,787 3/ 1943 Switzerland.

OTHER REFERENCES Billmeyer, Textbook of Polymer Chemistry, Interscience Publishers, New York (1957), pp. 254-255.

Sorenson et al.: Preparation Methods of Polymer Chemistry, Interscience Publishers, New York (1961), pp. 149- 151, 158-160, 162-165 and 178-179.

ALBERT T. MEYERS, Primary Examiner V. C. CLARKE, Assistant Examiner US. Cl. X.R. 26080; 424- UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3,472 ,243 October 14 1969 Robert A. Wall et a1.

It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, lines 33 and 34, cancel "In addition, this overporous state with a harsh textureto'the hand.". Column 2, line 61, "cities" should read cites Column 3, line 1, cancel "to further insolubilize the polymerized vinylic formula" and inse are water soluble compounds of the general formula line 47 "cation" should read cations line 51, after "class" insert of line 55, "amide" should read amine line 70, "KmmC should read Kmn0 Column 4, line 53, "in" should read i Column 7, line 27, "nutreated" should read untreated Signed and sealed this 20th day of October 1970 (SEAL) Attest:

Edward M. Fletcher, Jr.

Attesting Officer Commissioner of Patents 

